Vitreous composition and articles made therefrom



Patented Jan. 19, 1926.

UNITED STATES EUGENE CHARLES BUCK, 01 NEW YORK, N. Y.

VI'IREOUB COMPOSITION AND ARTICLES MADE THEREFROM.

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Be it known ;that "I, -Eoom Cums boon, a citizen of the Grand Duchy of Luxembourg-and a resident of New York, in the county-of. New} York and State of New York, haveiiivented certain new and useful Improvements in'Viti-eous Com sitions and Articles Made Therefrom, of iv *ich- ,the following is a specification.

This invention relates to an improved vitreous composition and involves the provision of a glass composition having several important advantages and characteristics. One of the important advantages of the composition of the invention is its high resistance to the attack of hydrofluoric and fluosilicic acids. The invention'includes the improved vitreous composition and the process of making it. Y I have discovered that certain complex metaphosphate glasses derived from alumina and thealkali earth metal oxides are highly refractory toward hydrofluoric acid, and that, at the same time, these glasses have the proper plasticity within the range of temperature requisite for manipulation by blowing, pressing, rolling or similar operation's.

The improved vitreous composition of the invention is a complex metaphosphate of aluminum and one or more alkali earth metals, such as calcium or magnesium, in which the alkali earth metal is advantageously present in greater molecular ratio than the aluminum.

The invention ,will be more fully described in connection with the following illustrative-examples of glasses of composition typical of the invention. The first of the following tabulations gives the compo sitions of eight different glasses of the invention in percentage by weight, and the second gives the compositions of the same eight glasses in terms of the molecular ratios of the constituents.

Compositions in percentage by weight It will be noted that the amount of phosphoric acid (represented as the anhydride Application and February 26, 1924. Serial in. 895,141.

P 0 present in each of these glasses is suflicient to satisfy the requirements for the formation of the metaphosphate of the associated metal oxides. It will also be noted that the molecular ratio of basic components to the acidic components varies from 15:17 to 5:9, and that the molecular ratio of the alkali earth metal oxide .to the aluinina varies from 14 1 to 3 2. In the above glasses, the amount of alkali earth metal oxide variesfrom 32.56 parts to 1313 parts and the amount of alumina from 3.62 parts to 15.94 parts in compositions including 100 parts by weight of phosphoric anhydride.

The improved glass of the invention can be made by fusing in a fire clay crucible the calculated amounts of ingredients giving the desired composition, making the necessary allowances for losses during melting down of the crucible charge, such as volatilization of phosphoric acid. :The alkali earth metal-oxide, lime for example, may be incorporated into the batch, as the equivalent amount of the monophosphate, CaH (PO,) for example. The alumina may be introduced as such-or as the orthophosphate, AlPO The phosphoric acid required to form the complex metaphosphate of the invention may be added as phosphoric anhydride or as metaphosphoric acid,

(glassy phosphoric acid), making due a]- lowance for the phosphoric acid added in combination with the basic components.

In order to rid the molten glass of any traces of silica taken .up from the siliceous material of the crucible, generally less than 1%, an equivalent amount of a fluorine compound such as aluminum fluoride, cryolite or fiuorspar may be added to the batch during the course of the melting down operation. Where some silica is present in the fusing mass, the addition of a fluorine compound promotes the agitation of the batch due to the escaping bubbles of silicon fluoride vapors. The effect of any silica present can also be minimized by the addition of an excess of 'met-aphosphoric acid, at least equivalent to the silica present, which then combines with the si1ica,'apparently forming the monosilicyl phosphate, SiO,.P,O,.

The coefiicient of expansion of the'improved glass composition is lowered by the substitution of equivalent molecular amounts of magnesia for lime in the composition.

By altering the relative proportions of the alkali earth metal oxides present in the glass, a glass can be obtained having any desired coefficient of expansion intermediate the high value of a lime-alumina metaphosphate glass and the low value of a magnesia-alumma metaphosphate glass. The vitreous composition of the invention is useful as an enamel coat and re ulation of the coefficient of expansion in t is manner is sometimes advantageous in such appllcations.

This also enables the production of compound glasses, that is glasses Iormed of two or more moulded layers of difierent glasses but having substantially the same coeflicient of expansion. For example, a variety-of glass objects may be madebv either blowing, pressing or drawing, of which the 1nner or outer layer, as the. conditions may require, is a metaphosphate glass of the inventlon, and the other layer a siliceous glass, both layers having substantially the same coeflicient of expansion and the same range of workability.

The composition of the invention 18 particularly adapted for making glass ware such as bottles, dishes, stirrin rods, and tiles, where resistance to fluorlne aclds s required. The improved vitreous compos tion of the invention is also useful in applications where high resistance to the attack of phosphoric acid or the joint attack of phosphoric and hydrofluoric acids is necessar ' I-l aving thus described my invention, what I claim and desire to secure by Letters Patent is:

1. An improved vitreous composition comprising a fused complex metaphosphate of aluminum and an alkali earth metal substantially free from silica.

2. An improved vitreous composition comprising a fused complex metaphosphate of aluminum and an alkali earth metal, the alkali earth metal being present in greater molecular ratio than the aluminum, substantially free from silica.

3. A hydrofluoric acid resistant glasscomprisinga fused complex metaphosphate of alumina and an alkali earth metal oxide in which the molecular ratio of the alkali earth metal oxide to the alumina is at least 1.5 to 1 substantially free from silica.

1. A hydrofluoric acid resistant glass comprismg the fused metaphosphates of lime and a umma substantially free from silica.

f;- A hydrofluoric acid resistant glas c PIlSlIlg the fused metaphosphates of lime and alumina, the lime being present in greater molecular ratio than the alumina, substantially free from silica.

6. A hydrofluoric acid resistant glass comprising the fused metaphosphates of lime and alumina, containing for each 100 parts of'phosphoric anhydride by weight between 32.56 and 13.13 parts of lime and between 3.62 and 15.94 parts of alumina, substantiallyyfree from s1lica.

"An im roved vitreous composition comprising a used complex metaphosphate of aluminum and an alkali earth metal substantially free from silica and containing 'nionosilicyl phosphate.

method of making a metaphosphate glass which comprises fusing together alumina and an alkali earth metal oxide and suflicient )hosphoric anhydride to form the metaphosp iates of the associated oxides.

'9. A method of making a metaphosphate glass which comprises fusing to ether alumina and an alkali earth metal oxi e and at least enough of a phosphoric acid compound to form the metaphosphates of the associated oxides.

10. A method of making a metaphosphate glass which comprises fusing together alumina and a phosphoric acid compound contaimng an alkali earth metal oxide with at least enough of a phosphoric acid compound to form the metaphosphates of all oxides present.

11. A method of making a metaphosphate glass which comprises fusing together phosphoric acid compounds of alumina and alkali earth metal oxides and suflicient of a phosphoric acid compound to form 'the metaphosphates of the alumina and alkali earth metal oxides.

12. A method of making a metaphosphate glass which comprises fusing together alumina, alkali earth metal oxides and a phosphoric acld compound and adding a fluorine compound to the fusion.

13. An .im roved vitreous composition comprismg t e fused metaphosphates of alumina and at least two alkali earth metal oxides substantially free from silica.

14. An improved vitreous composition C0mp I1S1l1% the fused metaphosphates of alumina, 1me and magnesia substantially free from silica.

15. An im roved vitreous composition comprising t e fused metaphos hates of alumina and an alkali earth meta oxide.

In testimony whereof, I hereunto aflix my signature. 

